Effect of poly(ethylene oxide) on the rheological behavior of silica suspensions

The steady-shear viscosity, dynamic viscoelasticity, and sedimentation behavior were measured for silica suspensions dispersed in aqueous solutions of poly(ethylene oxide) (PEO). For suspensions prepared with polymer solutions in which the transient network is developed by entanglements, the viscosity at a given shear rate decreases, shows a minimum, and then increases with increasing particle concentration. Because the suspensions are sterically stabilized under the conditions where the particle surfaces are fully covered with by a thick layer of adsorbed polymer, the viscosity decrease can be attributed to the reduction of network density in solution. But under the low coverage conditions, the particles are flocculated by bridging and this leads to a viscosity increase with shear-thinning profiles. The polymer chains with high molecular weights form flexible bridges between particles. The stress-dependent curve of storage modulus measured by a stress amplitude sweep shows an increase prior to a drastic drop due to structural breakdown. The increase in elastic responses may arise from the restoring forces of extended bridges with high deformability. The effect of PEO on the rheological behavior of silica suspensions can be explained by a combination of concentration reduction of polymer in solution and flocculation by bridging.     

Influence of dispersion procedure on rheological properties of aqueous solutions of high molecular weight PEO

The linear and nonlinear viscoelastic behaviors of poly(ethylene oxide) (PEO) in aqueous media have been investigated as a function of concentration and molecular weight. A particular interest has been paid to study the effect of turbulent flow under stirring, inducing both shear and elongational stresses, on the rheological behavior of the polymer solutions. The comparison of intrinsic viscosity and viscoelastic properties between shaken and stirred PEO solutions is discussed at the molecular scale in terms of chain scission and aggregation. Results point out that the effect of the mechanical history on the rheological response of PEO solutions depends also on the concentration regime and molecular weight. Indeed, the influence of the dispersion procedure vanishes by decreasing both the concentration and the molecular weight.     

Micron-scale origin of the shear-induced structure in Laponite–poly(ethylene oxide) dispersions

We study the transient response to simple shear of aqueous dispersions of Laponite clay particles and poly(ethylene oxide) at concentrations for which shear induces structure in the form of a network of polymer–clay bonds. We examine the effects of shear on the structure at the micrometer length scale. Bulk rheometric measurements give the material’s response to step changes in shear rate. We find that a critical value of the shear rate separates two regions with different rheological behaviors. Static small-angle light scattering shows a corresponding qualitative change in the anisotropy of the dispersion under shear at the micron scale. We interpret our results in terms of the effects of shear on the interactions between clay particles and polymer chains and on the aggregation mechanisms in the dispersion.     

Rheological behavior of silica suspensions flocculated by bridging

The viscosity and stress relaxation behavior of silica suspensions in polyacrylamide (PAAm) solutions have been studied as a function of particle concentration, particle diameter, and molecular weight of PAAm by the use of a coaxial cylinder type rheometer. The effects of polymer adsorption on the flocculation of particles and the rheological behavior are discussed in terms of bridging. The suspensions of 10-nm silica are remarkably pseudoplastic because the particles are easily flocculated by bridging. The ability of PAAm to flocculate silica particles is very extensive at a molecular weight of 5.5 × 10⁶. For suspensions of 20-nm silica in a solution of PAAm with M_W = 5.5 × 10⁶ − 1 × 10⁷, the apparent viscosity irreversibly increases with shearing time at shear rates beyond a certain value. This may be due to the flocculation by the shear-induced bridging. The suspensions of 40-nm silica show similar flow behavior to the medium irrespective of molecular weight of PAAm. The bridging flocculation is not expected for large particles as one polymer molecule cannot bridge through many particles.     

The effect of dissolved polymers on the rheological properties of coating colours

Coating colours used for the coating of paper and board consist mainly of a mineral pigment, which is very often clay, a synthetic binder such as a styrenebutadiene latex, dispersion agents and water retention aids. The latter are often water soluble polymers. These polymers have a very strong influence on the rheological properties of the coating colours, both on the strain rate dependence of the apparent viscosity and on the viscoelasticity. The effects of two different grades of carboxymethylcellulose (CMC) and one grade of hydroxyethylcellulose (HEC), on the rheological properties at room temperature of a clay-based coating colour at pH 8, have been investigated. It is concluded that the high values of the dynamic modulus of the colours are due to interactions between the cellulose derivatives and the solid particles, i.e. mainly the clay particles. For HEC this interaction is associated with adsorption of the polymeric molecules on the clay particles. In the case of CMC, the adsorption is strongly retarded by the presence of the dispersant (a polyacrylate salt). It is suggested that the marked elasticity of the CMC-containing colour in addition to a possible polymer adsorption may be due to charge interactions and/or depletion flocculation. The effect of CMC and HEC on the water-retention properties of the colour is also discussed.     

Rheological characterization of carbon nanotubes/poly(ethylene oxide) composites

Rheological properties of poly(ethylene oxide) nanocomposites embedded with carbon nanotubes (CNTs) were investigated in the present study. It was found that the CNT nanocomposites had a higher effective filler volume fraction than the real filler volume fraction, which yielded a drastic enhancement of shear viscosity. As the CNT loading in the nancomposites increases, non-Newtonian behavior was observed at the low-shear-rate region in the steady shear experiments. Oscillatory dynamic shear experiments showed that more addition of the CNTs led to stronger solidlike and nonterminal behaviors. To identify a dispersion state of the CNTs, field emission scanning electron spectroscopy and transmission electron microscopy were adopted and thermal analysis was also performed by using differential scanning calorimetry. The existence of percolated network structures of the CNTs even at a low CNT loading was verified by rheological properties and electrical conductivities.     

Rheological characterization of bimodal colloidal dispersions

In order to investigate the effect of the particle size distribution on the rheological properties of concentrated colloidal dispersions both steady-state shear and oscillatory measurements have been performed on well-characterized bimodal dispersions of sterically stabilized PMMA particles. Replacing a minor amount of large particles by small ones in a concentrated dispersion, keeping the total effective volume fraction constant, decreases the viscosity quite drastically. On the other hand, replacing a small amount of small particles by big ones hardly effects the viscosity at all. This behavior can be attributed to the deformability of the stabilizing polymer layer. A procedure is proposed to calculate the limiting viscosities in a bimodal colloidal dispersion starting from the characteristics of the monodisperse systems. A good agreement has been obtained between the calculated values and the experimental results. The linear viscoelastic properties of the concentrated dispersions have been investigated by means of oscillatory measurements. The plateau values of the storage modulus for the bimodal dispersions decrease with an increasing fraction of the coarse particles. By substituting the bimodal dispersion by an equivalent monodisperse system the storage modulus can be superimposed on the values for the monodisperse suspensions when plotted as a function of the mean interparticle distance.     

Electrical double layer and rheological properties of yttria-stabilized zirconia suspensions in solutions of high molecular weight polyacrylic acid polymers

This work deals with the effect of the adsorption of two high molecular weight polyacrylic acid polymers (Carbopol) on the interfacial properties, and the rheology of aqueous zirconia suspensions. Since the Carbopol-covered particles can be thought of as soft colloids, Ohshimas theory was used to gain information on the surface potential and the charge density of the polymer layer (Ohshima H (1995) Electrophoretic mobility of soft particles. Colloids Surf A Physicochem Eng Aspects 103:249–255). The effect of the pH of the solution on the double layer characteristics is related to the different conformations of the adsorbed molecules provoked by the dissociation of the acrylic groups present in polymer molecules. The electrokinetic properties of the suspensions are studied for different pH and Carbopol concentrations in solution in order to investigate the possible stabilization of the suspensions by electrostatic repulsion between the particles. The rheological behavior of the suspensions was investigated in steady-state and dynamic conditions, and the corresponding yield stress and storage modulus were obtained in absence and presence of polymer in solution. The competition between bridging flocculation provoked by polymer adsorption and electrosteric stabilization determines the rheological properties of the suspensions. In the pH range investigated, bridging flocculation predominates at the neutral pH because of the graft of the uncoiled polymer to more than one particle, while at the extreme pH values (pH 3, pH 9) steric or electrosteric stabilization seems to be the predominant mechanism that explains the rheological results. These facts were confirmed by estimating the zirconia particle (or aggregate) diameter in the liquid medium by means of light scattering measurements.     

The effect of pH,ionic strength,and temperature on the rheology and stability of aqueous clay suspensions

The effect of pH level, ionic strength, and temperature on the theology and stability of aqueous suspensions of attapulgite clay was systematically investigated. A Rheometrics Mechanical Spectrometer with cone and plate fixtures was used to measure the steady shear viscosity of the system. The edge charges of the clay particles can be adjusted by changing the pH level of the suspending medium so as to influence the flocculation state and, consequently, the rheological behavior of the suspension. This pH effect may be counteracted by the ionic strength effect at both very high and very low pH levels where the ionic strength is high enough to cause flocculation of the electrostatically stabilized suspension. The temperature effect study indicates that the relative contribution of Brownian motion and shear flow to the viscosity is dependent on the flocculation state of the suspension.     

A thermodynamic approach to the rheology of highly interactive filler-polymer mixtures. Part II. Comparison with polystyrene/nanosilica mixtures

The dynamic properties as a function of frequency and strain amplitude, steady-state viscosity as a function of shear rate, and transient shear stresses at startup and cessation of shear flow of polystyrene (PS)/fumed silica mixtures of various concentrations were investigated. An abrupt change in the viscoelastic properties was noticed at a concentration above 1% by volume. Observations by means of scanning electron microscopy (SEM) indicate the presence of a three-dimensional network through the bridging of filler particles by the adsorbed polymer. The viscoelastic behavior is simulated utilizing a theory proposed in Part I (Havet and Isayev 2001) based on a double network created by the entangled polymer matrix and the adsorbed polymer with filler concentration taken into account through the bridging density of polymer-filler interactions and a hydrodynamic reinforcement. The steps taken for determining the model parameters required to carry out the simulation are described. The major features of the rheological behavior of highly interactive polymer-filler mixtures are captured qualitatively and in some cases, quantitatively predicted.     

Evidence for re-entrant behavior in laponite–PEO systems

We observe evidence of re-entrant behavior in dispersions of a discotic clay, laponite, with added polymer. Under basic conditions, neat laponite forms a disordered colloidal glass. Rheologically, this phase behaves as a viscoelastic solid, and dynamic light scattering shows evidence of non-ergodic behavior. Addition of low molecular weight poly(ethylene oxide) (PEO) melts the glass, resulting in a low-viscosity liquid with fast dynamics. We believe this is due to a depletion force caused by excess PEO chains in solution. A viscoelastic solid is re-formed with the addition of high molecular weight PEO, which we believe to be caused by polymer chains bridging between laponite particles. The physics in our system is quite different from the hard sphere/nonadsorbing polymer systems for which re-entrant glass transitions have been reported in the literature; however, we believe there may be similarities between these phenomena. To our knowledge, this is the first evidence of a type of re-entrant behavior in anisotropic colloids.     

Shear-thickening and structure formation in polymer solutions

The phenomenon of shear-thickening has been investigated for solutions of several high molecular weight crystallizable polymers using capillary rheometry. The systems studied: polyethylene/xylene, polypropylene/tetralin, and poly(ethylene oxide)/ethanol have previously been investigated for their flow induced crystallization behavior. A shear-thickening pattern occurs in the relative viscosity vs. shear rate flow curves for the first two systems which, for the former of the two, also shows a strong molecular weight dependence. For the range of conditions studied, the poly(ethylene oxide)/ethanol system did not show shear-thickening, exhibiting instead a shear thinning pattern for the lower molecular weight sample studied and a constant viscosity high shear plateau for the higher MW system. The conclusion is reached that shear-thickening is due to molecular entanglements formed during flow and the implications of these results to the phenomenon of precursor phase separation in flow-induced fibrous crystallization are discussed.     

Measurements and model predictions of transient elongational rheology of polymeric nanocomposites

Transient elongational rheology of two commercial-grade polypropylene (PP) and the organoclay thermoplastic nanocomposites is investigated. A specifically designed fixture consisting of two drums (SER Universal Testing Platform) mounted on a TA Instruments ARES rotational rheometer was used to measure the transient uniaxial extensional viscosity of both polypropylene and nanoclay/PP melts. The Hencky strain rate was varied from 0.001 to 2 s^− 1, and the temperature was fixed at 180°C. The measurements show that the steady-state elongational viscosity was reached at the measured Hencky strains for the polymer and for the nanocomposites. The addition of nanoclay particles to the polymer melt was found to increase the elongation viscosity principally at low strain rates. For example, at a deformation rate of 0.3 s^− 1, the steady-state elongation viscosity for polypropylene was 1.4 × 10⁴ Pa s which was raised to 2.8 × 10⁴ and 4.5 × 10⁴ Pa s after addition of 0.5 and 1.5 vol.% nanoclay, respectively. A mesoscopic rheological model originally developed to predict the motion of ellipsoid particles in viscoelastic media was modified based on the recent developments by Eslami and Grmela (Rheol Acta 47:399–415, 2008) to take into account the polymer chain reptation. We show that the orientation states of the particles and the rheological behavior of the layered particles/thermoplastic hybrids can be quantitatively explained by the proposed model.     

Rheological behavior of filled propylene/ethylene copolymers

A new family of propylene-ethylene copolymers developed by The Dow Chemical Company has narrow molecular weight distributions for industrial polymers and broad chemical composition distributions. This molecular architecture makes possible high filler loadings while maintaining good processability. To provide a fundamental understanding of the lower than expected viscosity, a study of the shear rheological behavior of two series of composites was performed. The composites consist of stearate-coated calcium carbonate particles suspended in a propylene-ethylene copolymer. The matrix in one series was a new copolymer, and in the other series, it was a traditional metallocene copolymer. For both systems, the viscosity increases dramatically with increasing filler loading; however, the viscosity is lower in the case of the composites of the new copolymer. The stearate coating on the calcium carbonate particles decreases the adhesion of the polymer to the filler surface, allowing particle-matrix interfacial slip. A high temperature atomic force microscopy study has indicated the existence of ethylene-enriched zones in the matrix immediately surrounding the particles in the new copolymer. We hypothesize that these high ethylene content chains around the particle surface enhance particle-matrix interfacial slip resulting in the lower composite viscosity.     

Brownian dynamics simulation of multiphase suspension of disc-like particles and polymers

A computational model is proposed for simulating the flow of polymer nanocomposites. This model is based on a multiphase suspension of disc-like particles and polymers. The particles are represented by oblate spheroid particles that interact with each other via the Gay-Berne (GB) potential, and the polymers are modeled by finitely extensible nonlinear elastic (FENE) chains that interact with each other via the repulsive Lennard-Jones potential. The interaction between an oblate spheroid particle and a FENE chain is also considered using a modified GB potential. A Brownian dynamics simulation of the shear flows of this system was conducted to investigate the orientation behavior of disc-like particles and the rheological properties of this system. The orientation of disc-like particles was affected by polymers, and the particles in a suspension were well aligned in flows because of the flow orientation property of polymers. The predicted shear viscosity exhibited shear thinning, and the normal stress differences agree qualitatively with experimental measurements of polymer/clay nanocomposites. The simulation results suggest that the present model has the potential to be used as a computational model for polymer nanocomposites.     

Linear viscoelastic master curves of neat and laponite-filled poly(ethylene oxide)–water solutions

Aqueous solutions composed of dispersed nanoparticles and entangled polymers are shown to exhibit common viscoelasticity over a range of particle and polymer concentrations. Time–temperature superposition and time–concentration superposition are applied to generate rheological master curves for neat and laponite-filled aqueous solutions of poly(ethylene oxide). The shift factors were correlated in terms of temperature and concentration and are found to differ from previous reports for ideal polymer solutions, which can be rationalized with a molecular interpretation of the structure of the laponite–polymer solutions. Laponite addition to the concentrated polymer solution is observed to increase the relaxation time but decrease the elastic modulus, which is a consequence of polymer adsorption and bridging. The addition of small amounts of laponite to stable PEO–water solutions also leads to ageing on the time scale of days.     

活性流体流变行为的布朗动力学模拟研究

活性流体在用于开发新材料方面具有巨大潜力, 满足这一需求就要定量掌握活性流体所表现的特殊力学行为, 特别是流变行为. 扩展布朗运动方程, 建立自驱动活性粒子的运动模型, 基于反向非平衡法确定活性流体的黏度, 考察活性粒子体积分数、直行速度和转向扩散系数对活性流体流变行为的影响规律, 确定活性流体特殊流变行为的形成机理. 结果表明, 活性流体的流变曲线可被划分为黏度下降区、过渡区和牛顿区; 活性粒子体积分数越高, 活性流体的非牛顿特性越显著, 活性粒子的直行运动引起活性流体在低剪切速率区域黏度下降, 直行运动和转向运动的耦合作用导致中剪切速率区域流变曲线非单调变化, 活性粒子频繁发生转向运动会导致活性流体非牛顿特性受到抑制; 活性流体的宏观流变学特性和粒子的涨落直接相关, 活性粒子体积分数越高、直行速度越快和转向扩散系数越小, 活性流体中活性粒子越容易产生显著的涨落; 低剪切速率区域内活性粒子涨落明显, 随着剪切速率增大, 活性粒子的涨落逐渐被削弱, 粒子的聚集结构不断被破坏, 最终体系的流变行为类似一般被动流体.      

Rheomechanical and morphological study of compatibilized PP/EVOH blends

In order to find the relationships between processibility and properties of the polypropylene/ethylene vinyl alcohol copolymer (PP/EVOH) blends, their rheological behavior, in both shear and extensional flows, was studied and related with mechanical, morphological, and barrier properties of the materials. The nonlinear viscoelastic behavior in shear was also analyzed. The data showed that the rheological parameters (viscosity, loss modulus, storage modulus, extensional viscosity, and Trouton ratio) improved with the addition of low quantities of sodium ionomer copolymer used as compatibilizer. At the same time, the overall properties of the PP/EVOH blends improved as a result of the compatibilizer addition. The morphological analysis showed that the changes in the material properties were related with a more uniform distribution of EVOH particles in the PP matrix. The rheological data obtained allowed us to choose the optimal range for EVOH and ionomer contents, especially in terms of combining good processing characteristics with the good final properties.     

Long-term aging effects on the rheology of neat laponite and laponite–PEO dispersions

We observe aging behavior of neat laponite systems over the course of 1,000 or more days. Under basic conditions, low laponite concentrations (1 wt%) slowly evolve from a viscoelastic liquid to a glass made of clusters acting as constituent elements interacting via long-range repulsion. Higher concentrations of laponite (3 wt%) quickly form a glass of individual particles. Intermediate concentrations of laponite form a glass that is a combination of clusters and individual particles. The aging rheological response and upturn of the loss modulus at low frequencies are well predicted by models of soft glassy systems (Fielding et al., J Rheol, 44(2):323–369, 2000; Sollich, Phys Rev E, 58(1):738–759, 1998). If low amounts of high-molecular-weight (M _n ≥ 163 kg/mol) poly(ethylene oxide) (PEO) are added, the aging behavior follows the dynamical response of the clay. Above a critical ratio, φ, of the free polymer chains in solution to the total laponite surface area, the PEO dynamics dominate at high frequencies. It appears that the dynamics of these complex laponite-PEO systems are governed by the parameter φ.     

Characterization of polymer dispersions by Fourier transform rheology

Fourier transform rheology is a very sensitive technique to characterize non-linear rheological fluid properties. It has been applied here for the first time to polymer dispersions in water and the results are compared to those from conventional rheology, namely steady and small amplitude oscillatory shear experiments. The investigated systems are mainly based on styrene and n-butylacrylate. A first attempt was made to evaluate how far colloidal parameters like particle volume fraction and ionic strength as well as chemical composition and surface characteristics of the dispersed particles are reflected in FT-rheology spectra. Significantly different non-linearities are observed for highly concentrated dispersions of particles with different T_g. These differences are not detected in linear oscillatory shear and show up in steady shear only at significantly higher shear rates. Particle surface characteristics influence the non-linear response in oscillatory shear significantly and the intensity of the overtones is found to be higher for a dispersion of particles with a “hairy” swollen surface layer as compared to a system of smooth particles, although the solids content was adjusted to match the steady shear viscosity. The intensity of the overtones in FT-rheology strongly decrease upon dilution. At a solid content below 35% no differences are observed in the FT-experiments for the systems investigated here, whereas the differences in steady shear are very pronounced in this concentration range. A significant influence of added salt onto the non-linear response is detected for some systems, which might be correlated to the stability of these systems. The observed phenomena certainly cannot be explained in terms of constitutive equations or microstructural statistical mechanical models at present. Thus, FT-rheology yields information complementary to classical steady or linear oscillatory shear experiments. Received: 11 December 2000 Accepted: 8 April 2001